Crystalline mixture solid composition and preparation thereof

ABSTRACT

A crystalline mixture solid composition comprising α-D-glucopyranosyl-1,1-mannitol (GPM), α-D-glucopyranosyl-1,6-sorbitol (GPS-6) and a small amount of α-D-glucopyranosyl-1,1-sorbitol (GPS-1) and a production process therefor. The above crystalline mixture solid composition is produced by mixing a hydrophilic solvent with a solid composition or aqueous solution comprising 50 to 80 wt % of GPM, 1 to 50 wt % of GPS-6 and 0.01 to 20 wt % of GPS-1, separating solid matter from a liquid, and removing water and the solvent from the solid matter and can be obtained as a thin scale crystal.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a crystalline mixture solid compositionwhich comprises α-D-glucopyranosyl-1,1-mannitol andα-D-glucopyranosyl-1,6-sorbitol and/or a small amount ofα-D-glucopyranosyl-1,1-sorbitol and to a production process therefor.

2. Prior Art

Hydrogenated isomaltulose (hydrogenated palatinose) has been known asone of low-calorie sweeteners which do not cause a carious tooth. Thehydrogenated isomaltulose is a mixture of two sugar alcohols, that is,an almost equimolar mixture of α-D-glucopyranosyl-1,1-mannitol (to beabbreviated as GPM hereinafter) and its isomerα-D-glucopyranosyl-1,6-sorbitol (to be abbreviated as GPS-6hereinafter), which can be obtained by forming isomaltulose (palatinose)from cane sugar by means of a transferase and then hydrogenating thepalatinose.

The hydrogenated isomaltulose is known as an extremely useful sweetenerwhich exhibits an excellent sweet taste like cane sugar, has lowhygroscopicity, heat resistance, acid resistance, alkali resistance,excellent processability such as tablettability and granulability, andphysiological properties such as low calorie, noncariogenic propertiesand insulin non-irritating properties.

As the method of crystallizing the hydrogenated isomaltulose, H.Schiweck's report (Alimenta. 19,5-16,1980) discloses a vacuumcrystalizar process. However, this process is very complicated andrepeats the steps of evaporation, aging and centrifugation, therebyconsuming a huge amount of energy and boosting product costs.

JP-A 60-181094 (the term “JP-A” as used herein means an “unexaminedpublished Japanese patent application”) discloses a process forcrystallizing an aqueous solution of hydrogenated isomaltulose having asolid content of about 80% in a vacuum crystallization apparatus.However, since this process requires a special apparatus such as avacuum crystallization apparatus and employs a batch system, it is notpractical due to its low production efficiency.

JP-A 62-148496 discloses a process for crystallizing hydrogenatedisomaltulose in accordance with a kneading method using seed crystals.This process is used to crystallize mainly a GPM component out ofhydrogenated isomaltulose components. That is, the water content of thehydrogenated isomaltulose is adjusted to a range of more than 5% and 20%or less, the liquid temperature is maintained at a range of 50 to 90° C.according to the content of water, seed crystals are added and mixed,and the mixed product is solidified by cooling the temperature at aroundroom temperature, dried and ground to obtain crystallized hydrogenatedpalatinose powders. However, this process has a problem with processing(such as grindability) as the kneaded product obtained by this processhas high stickiness and also a problem with distribution (such as cakingand the propagation of microorganisms) as cooling and drying take longtime.

It is also known that when a transferase is caused to act on cane sugar,trehalulose (α-D-glucopyranosyl-1,1-fructose) is formed in addition toisomaltulose. Generally speaking, when hydrogenated isomaltulose isproduced, after only isomaltulose is obtained by crystallizationseparation, the residual mixture containing trehalulose is discarded ordisposed at a low cost. It is known that trehalulose is converted intoGPM and α-D-glucopyranosyl-1,1-sorbitol (to be abbreviated as GPS-1) byhydrogenation. That is, when a transferase is caused to act on canesugar as a raw material and the obtained mixture is hydrogenated, amixture of GPM, GPS-6 and GPS-1 can be obtained. To obtain such amixture, a process is known as disclosed in JP-A 7-51079. This processcomprises the first step of carrying out the conversion reaction of canesugar, the second step of removing unreacted cane sugar and the thirdstep of carrying out a hydrogenation reaction in the presence of acatalyst. As for solidification, the above publication discloses a fineparticulate product obtained by vaporizing water for solidification andgrinding. However, the product is an amorphous and glass-like solid, hashigh hygroscopicity, and is difficult to handle and easily worn byabrasion during circulation. Generally speaking, when the content of ahoney portion (GPS-1 and the residual sugars in the present invention)in a crystalline mixture solid is high, the product has high moistureabsorption and is difficult to handle. Consequently, a crystallinemixture solid composition which has a low content of the honey portionand excellent handling ease and can be produced at a low cost has beendesired.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a crystallinemixture solid composition which rarely has moisture absorption, is easyto handle and dissolve, and comprises GPM and GPS-6 and/or a smallamount of GPS-1 in an extremely short period of time with small-scaleequipment by a process which can save power and does not take much timeand labor.

It is another object of the present invention to provide an industriallyadvantageous process for producing the above crystalline mixture solidcomposition of the present invention.

Other objects and advantages of the present invention will becomeapparent from the following description.

According to the present invention, firstly, the above objects andadvantages of the present invention are attained by a crystallinemixture solid composition which comprisesα-D-glucopyranosyl-1,1-mannitol, α-D-glucopyranosyl-1,6-sorbitol and0.01 to 1.99 wt % of α-D-glucopyranosyl-1,1-sorbitol (the above wt % isbased on the total weight of the α-D-glucopyranosyl-1,1-mannitol,α-D-glucopyranosyl-1,6-sorbitol and α-D-glucopyranosyl-1,1-sorbitol)(may be referred to as “first crystalline mixture solid composition ofthe present invention” hereinafter).

According to the present invention, secondly, the above objects andadvantages of the present invention are attained by a thin scalecrystalline mixture solid composition which comprisesα-D-glucopyranosyl-1,1-mannitol and α-D-glucopyranosyl-1,6-sorbitol (maybe referred to as “second crystalline mixture solid composition of thepresent invention” hereinafter).

According to the present invention, thirdly, the above objects andadvantages of the present invention are attained by a process forproducing a crystalline mixture solid composition, comprising the stepsof supplying a composition comprising 50 to 80 wt % ofα-D-glucopyranosyl-1,1-mannitol, 1 to 50 wt % ofα-D-glucopyranosyl-1,6-sorbitol and 0.01 to 20 wt % ofα-D-glucopyranosyl-1,1-sorbitol into a kneader to knead and cool it soas to produce a composition, mixing the composition with a hydrophilicsolvent, separating solid matter from a liquid, and removing water andthe solvent from the solid matter (the above wt % is based on the totalweight of the α-D-glucopyranosyl-1,1-mannitol,α-D-glucopyranosyl-1,6-sorbitol and α-D-glucopyranosyl-1,1-sorbitol)(may be referred to as “first production process of the presentinvention” hereinafter).

According to the present invention, fourthly, the above objects andadvantages of the present invention are attained by a process forproducing a crystalline mixture solid composition, comprising the stepsof mixing an aqueous solution containing 50 to 80 wt % ofα-D-glucopyranosyl-1,1-mannitol, 1 to 50 wt % ofα-D-glucopyranosyl-1,6-sorbitol and 0 to 20 wt % ofα-D-glucopyranosyl-1,1-sorbitol with a hydrophilic solvent, separatingthe formed precipitate from a liquid, and removing water and the solventfrom the precipitate (the above wt % is based on the total weight of theα-D-glucopyranosyl-1,1-mannitol, α-D-glucopyranosyl-1,6-sorbitol andα-D-glucopyranosyl-1,1-sorbitol) (may be referred to as “secondproduction process of the present invention” hereinafter).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an electron photomicrographic diagram of a crystalline mixturesolid composition obtained in Example 3 (magnification of ×500);

FIG. 2 is an electron photomicrographic diagram of a crystalline mixturesolid composition obtained in Example 3 (magnification of ×1,000);

FIG. 3 is an electron photomicrographic diagram of composition X(magnification of ×500);

FIG. 4 is an electron photomicrographic diagram of composition X(magnification of ×1,000);

FIG. 5 is an electron photomicrographic diagram of composition Y(magnification of ×X500);

FIG. 6 is an electron photomicrographic diagram of composition Y(magnification of X1,000);

FIG. 7 is an X-ray diffraction diagram of a crystalline mixture solidcomposition obtained in Example 2;

FIG. 8 is an X-ray diffraction diagram of composition X;

FIG. 9 is an X-ray diffraction diagram of composition Y; and

FIG. 10 is a differential scanning calorimeter analytical diagram of acrystalline mixture solid composition.

THE PREFERRED EMBODIMENT OF THE INVENTION

The present invention will be described in detail hereinbelow. Adescription is first given of the first production process and the firstcrystalline mixture solid composition of the present invention.

In the first production process, as described above, a solidifiedmixture containing 50 to 80 wt % of GPM, 1 to 50 wt % of GPS-6 and 0.01to 20 wt % of GPS-1 is used as a raw material.

As the raw material is used a crystalline mixture solid compositionproduced by solidifying a mixed solution prepared by hydrogenating amixture of isomaltulose and trehalulose obtained by causing atransferase to act on cane sugar. In the first production process, thecrystalline mixture solid composition of the present invention isproduced by mixing this composition with a hydrophilic solvent,separating solid matter from a liquid, and removing water and thesolvent from the solid matter.

The preferred contents of isomaltulose and trehalulose beforehydrogenation are 5 to 100 wt % and 0 to 95 wt %, respectively.

The crystalline mixture solid composition of the present invention isproduced from a mixture containing isomaltulose and trehalulose producedfrom cane sugar through an isomerization reaction before hydrogenationas described above. Impurities may be separated from the mixture as theraw material.

The transferase is a bacteria which is generally used for the productionof isomaltulose, an enzyme extracted from the bacteria, or animmobilized product thereof, such as a bacteria which belongs to thegenus of Protaminobacter, Serratia, Erwinia, Klebsierra, Pseudomonas,Agrobacterium or Leuconostoc.

To solidify a mixed solution of GPM, GPS-6 and GPS-1 by using a kneader,it is preferably solidified as a powdery crystalline mixture solidcomposition by supplying it into an extruder (kneader) having a slendercooling/kneading zone, kneading, cooling and extruding it through apunching plate, and cooling and grinding the extruded product.

The above mixed solution is supplied at preferably approximately 70 to140° C., more preferably approximately 90 to 130° C. in consideration offluidity for achieving handling ease and control ease for the formationof a magma. The temperature of a cooled portion for the formation of amagma may be adjusted to a temperature at which crystallization heatgenerated can be removed, preferably 100° C. or less, more preferably70° C. or less.

The feed rate of the mixed solution into the kneader differs accordingto the type and capacity of the kneader in use. For example, when theKRC kneader (2S) of Kurimoto Ironworks Co., Ltd. is used, the mixedsolution may be fed at a rate of 2 to 50 kg/hr.

To produce the crystalline mixture solid composition of the presentinvention, a seed crystal may be used in combination with the rawmaterial composition. The seed crystal used at this point may be a seedcrystal with which the mixed solution of GPM, GPS-6 and GPS-1 iscrystallized in the kneader, for example, a crystal powder having almostthe same composition (GPM/GPS-6/GPS-1) as that of the raw material mixedsolution, or a seed crystal obtained by recycling a crystalline mixturesolid composition produced by the present invention. The addition rateof the seed crystal is preferably approximately 0.1 to 25 kg/hr. Theamount of the seed crystal added is not particularly limited but it isgenerally approximately 2 to 50 wt %, preferably approximately 5 to 40wt % based on the raw material in consideration of crystallization speedand cost.

The kneader which can be used in the present invention may be of acontinuous or batch system. A closed type kneader which is capable ofkneading and cooling at the same time and can extrude the kneadedproduct continuously from a discharge port after kneading and cooling ispreferred. Examples of the kneader include an extruder, continuouskneader, mixtron and kneadex. Out of these, an extruder is preferred.Examples of the extruder include KRC kneader (of Kurimoto Ironworks,Co., Ltd.), double-screw extruder for food (of Nippon Steel Co., Ltd.)and double-screw cooking extruder (of W & P Co., Ltd. of Germany).

When a magma is to be discharged from a continuous kneader, the shape ofthe magma may be selected from noodle-like, ribbon-like, rod-like andplate-like shapes, out of which noodle-like and ribbon-like shapes arepreferred in consideration of subsequent cooling and grinding steps. Apunching plate installed at the discharge port preferably has a porediameter of approximately 2 to 5 mm and a porosity of approximately 10to 40%.

The cooling method is not particularly limited. For example, the magmadischarged from the kneader may be directly exposed to cool air, themagma may be left at the room temperature or the magma may be cooled toapproximately room temperature on a metal net belt with cool air.

The obtained crystalline mixture solid composition is powdered bygrinding. The grinding method is not particularly limited and a commonlyused grinder may be used to grind the crystalline mixture solidcomposition.

The thus obtained powdery crystalline mixture solid composition containswater equivalent to the water of crystallization of GPM, for example,and mixed with a hydrophilic solvent. Preferably, the hydrophilicsolvent preferably has lower solvency for GPM and GPS-6 than solvencyfor GPS-1. Examples of the hydrophilic solvent are aliphatic alcoholshaving 1 to 4 carbon atoms, acetone, aliphatic carboxylic acids having 1to 3 carbon atoms, acetonitrile and pyridine. They may be used alone orin combination of two or more. Out of these, ethanol, methanol, acetoneand n-propanol are preferred and ethanol is particularly preferred asthe hydrophilic solvent.

When ethanol is used as the hydrophilic solvent, the concentration ofethanol is preferably approximately 60 to 90%. The amount of thehydrophilic solvent at the time of mixing is preferably approximately 2to 10 times the amount of the solid matter. As for the stirring time andstirring speed, when stirring is carried out using a 6-blade turbine,the stirring time is preferably approximately 10 to 180 minutes and thestirring speed is preferably approximately 10 to 300 rpm.

To separate the solid matter or precipitate from a liquid after mixing,a general separation method such as suction filtration or centrifugalseparation is employed. The solid matter after separation may begranulated as it is or by a granulator which is generally used after itis dried and the solvent is removed as required.

The above first crystalline mixture solid composition of the presentinvention is advantageously produced by the first process of the presentinvention.

The first crystalline mixture solid composition of the present inventioncomprises GPS-1 in an amount of preferably 0.01 to 1.5 wt %, morepreferably 0.01 to 1.0 wt %.

A description is subsequently given of the second production process andthe second crystalline mixture solid composition of the presentinvention.

The second production process of the present invention differs from thefirst production process in the following points. The solid mattercontaining GPM, GPS-6 and GPS-1 is mixed with the hydrophilic solvent inthe first production process whereas an aqueous solution containing GPMand GPS-6 and/or GPS-1 is mixed with the hydrophilic solvent in thesecond production process. Commercially available hydrogenatedisomaltulose may be used in the second production process. This aqueoussolution has a solids content of preferably about 10 to 90 wt %, morepreferably 20 to 80 wt %, particularly preferably 50 to 70 wt %. To mixtogether the aqueous solution and the hydrophilic solvent, thehydrophilic solvent may be added to the aqueous solution, or the aqueoussolution may be added to the hydrophilic solvent. Alternatively, theymay be added and mixed together at the same time. It should beunderstood that the above description of the first production process isapplied to what is not described of the second production processdirectly or with modifications which are obvious to one of ordinaryskill in the art.

The above second crystalline mixture solid composition of the presentinvention, that is, a crystalline mixture solid composition which is anaggregate of thin scale crystal particles is advantageously produced bythe second production process of the present invention.

When the second crystalline mixture solid composition of the presentinvention contains GPS-1, the amount of GPS-1 is preferably 5 wt % orless, more preferably 2 wt % or less, much more preferably 1 wt % orless.

Preferably, the second crystalline mixture solid composition of thepresent invention comprises particles having a particle diameter of 60Tyler mesh or less in an amount of at least 70 wt % of the total. Thespecific surface area of the second crystalline mixture solidcomposition is preferably 0.5 to 5.0 m²/g, more preferably 0.5 to 2.0m²/g.

The packed bulk density (apparent specific gravity) of the secondcrystalline mixture solid composition of the present invention ispreferably 0.2 to 0.6 g/cc, more preferably 0.3 to 0.5 g/cc.

When the second crystalline mixture solid composition of the presentinvention was observed through a ×500 or ×1,000 scanning electronmicroscope, a thin scale crystal structure was observed. When the secondcrystalline mixture solid composition of the present invention wascompared with a solidified product of the raw material of the firstcrystalline mixture solid composition of the present invention andcommercially available hydrogenated isomaltulose, it was confirmed thatthe composition differed from them in surface structure. It is alsoconsidered from the measurement results obtained by an X-ray diffractionmeasuring instrument and differential scanning calorimeter that thesecond crystalline mixture solid composition of the present inventionhas a different crystal structure from that of the prior art.

According to the present invention, there can be obtained a high-qualitypowdery or granular crystalline mixture solid composition which is easyto handle and soluble.

The present invention will be described in detail hereinbelow withreference to Examples and Comparative Examples. “%” in the Examplesmeans “wt %”.

EXAMPLES Example 1

(Process)

(1) A sugar alcohol mixed solution containing 56.0% of GPM, 37.5% ofGPS-6, 3.0% of GPS-1 and 3.5% of other sugars (mainly sorbitol andmannitol) was concentrated to a solids content of 94% and thisconcentrated solution was injected into a continuous closed kneader(S2-KRC kneader: manufactured by Kurimoto Ironworks, Co., Ltd., jackettemperature of 10° C., revolution of 60 rpm) together with 20 wt % of aseed crystal (trade name: ISOMALT TypeM, manufactured by Palatinit Co.,Ltd.; spherical solid grain having a diameter of 0.5 to 4.5 mm andcontaining about 52.3% of GPM and about 47.1% of 1,6-GPS) based on thetotal amount while it was maintained at 120° C., kneaded and cooled. Thekneaded product was extruded at a rate of 18 kg/hr through a punchingplate having a diameter of 5 mm, and the extruded product was cooled andground by a grinder (POWER MILL (TYPE P-3): manufactured by Showa KagakuKikai Kosakusho Co., Ltd.) to prepare a powdery crystalline mixturesolid composition having a water content of 5.7%. (2) 100 g of thepowdery crystalline mixture solid composition obtained in (1) above wasadded to 350 g of a 80% ethanol aqueous solution contained in a flaskand stirred at 30° C. for 30 minutes, and the obtained slurry wasseparated into solid matter (powder) and a liquid by suction/filtration.The recovered solid matter was dried with a drier heated at 60° C. for180 minutes to remove the solvent to obtain a powdery crystallinemixture solid composition having no moisture absorption.

(Results)

The sugar composition, solids content and solids yield of the obtainedpowdery crystalline mixture solid composition are shown in Table 1.

TABLE 1 sugar composition (% · solids content) solids solids othercontent yield GPM GPS-6 GPS-1 sugars (%) (%) raw 56.0 37.5 3.0 3.5 94.3— material Ex. 1 59.4 39.1 0.9 0.6 94.0 89.0 (59.8) (39.3) (0.9) Ex.:Example *The figures within the parentheses in the table are theproportions of GPM, GPS-6 and GPS-1.

Example 2

(Process)

155.5 g of an aqueous solution obtained by concentrating the rawmaterial sugar alcohol solution used in Example 1 to a solids content of60% was added to 590.9 g of a 88% ethanol aqueous solution (finalethanol concentration was 80%). They were stirred at 30° C. for 30minutes and the resulting solution was separated into a precipitate anda liquid by suction/filtration. The recovered precipitate was dried inthe same manner as in Example 1 to obtain a powdery crystalline mixturesolid composition having no moisture absorption.

(Results)

The sugar composition, solids content and solids yield of the obtainedpowdery crystalline mixture solid composition are shown in Table 2.

TABLE 2 sugar composition (% · solids content) solids solids othercontent yield GPM GPS-6 GPS-1 sugars (%) (%) raw 56.0 37.5 3.0 3.5 60.0— material Ex. 2 60.3 41.9 0.7 2.8 99.0 81.8 (58.6) (40.7) (0.7) Ex.:Example *The figures within the parentheses in the table are theproportions of GPM, GPS-6 and GPS-1

Example 3

(Process)

63.5 g of an aqueous solution obtained by concentrating the raw materialsugar alcohol solution used in Example 1 to a solids content of 70% wascooled to 30° C. and 136.5 g of a 91.2% ethanol aqueous solution (finalethanol concentration was 80%) was added to the aqueous solution over 60minutes under stir. After the addition of the ethanol aqueous solution,the resulting solution was separated into a precipitate and a liquid bycentrifugal filtration. The recovered precipitate was dried in the samemanner as in Example 1 to obtain a powdery crystalline mixture solidcomposition having no moisture absorption.

(Results)

The sugar composition, solids content and solids yield of the obtainedpowdery crystalline mixture solid composition are shown in Table 3.

TABLE 3 sugar composition (% · solids content) solids solids othercontent yield GPM GPS-6 GPS-1 sugars (%) (%) raw 56.0 37.5 3.0 3.5 60.0— material Ex. 3 57.6 35.6 0.8 6.0 93.8 90.5 (61.3) (37.9) (0.8) Ex.:Example *The figures within the parentheses in the table are theproportions of GPM, GPS-6 and GPS-1

Example 4 and Comparative Examples 1 and 2

(Process)

Pt-Pb was deposited on the powdery crystalline mixture solid compositionobtained in Example 2, a solidified product of the raw material sugaralcohol mixed solution used in Example 1 (composition X) and acommercially available hydrogenated isomaltulose powder (composition Y)for 60 seconds and the obtained products were observed through ascanning electron microscope (S-4300: Hitachi, Ltd.) under a voltage of1 kV.

(Results)

It was confirmed that the crystalline mixture solid composition obtainedin Example 2 consisted of homogeneous thin scale crystals. FIG. 1 andFIG. 2 show ×500 and ×1,000 electron photomicrographs of thecomposition. FIG. 3 and FIG. 4 show ×500 and ×1,000 electronphotomicrographs of Comparative Example 1 and FIG. 5 and FIG. 6 show×500 and ×1,000 electron photomicrographs of Comparative Example 2.

Example 5 and Comparative Examples 3 and 4

The powdery crystalline mixture solid composition obtained in Example 2,the composition X and the composition Y were ground and sieved tomeasure the specific surface area and packed bulk density (apparentspecific gravity) of what passed through a 60-mesh sieve.

(Method)

Specific Surface Area

The sample was dried at room temperature for 1 hour and used for themeasurement of its specific surface area with the Monosobe MS-17(manufactured by Yuasa Ionics Co., Ltd.).

Packed Bulk Density (Apparent Specific Gravity)

This was measured using a powder tester (PT-N: manufactured by HosokawaMicron Co., Ltd.) (180 times of tapping).

(Results)

The obtained results are shown in Table 4.

TABLE 4 Ex. 5 C. Ex. 3 C. Ex. 4 specific surface area (m²/g) 0.91 0.140.40 packed bulk density (g/cc) 0.41 0.65 0.79 (apparent specificgravity) Ex.: Example C.Ex.: Comparative Example *Each value is the meanof three measurement values.

Test Example

(Measurement with X-ray Diffraction Measuring Instrument)

The powdery crystalline mixture solid composition obtained in Example 2,the crystalline mixture solid composition of Comparative Example 1 andthe hydrogenated isomaltulose powder of Comparative Example 2 weremeasured with an X-ray diffraction measuring instrument (MiniFlex:manufactured by Rigaku Co., Ltd.) at a scanning axis of θ/2θ, ameasurement angle of 3 to 90° and a sampling axis of 0.01°. Themeasurement results are shown in FIG. 7, FIG. 8 and FIG. 9.

(Measurement with Differential Scanning Calorimeter)

The powdery crystalline mixture solid compositions obtained in Examples1 and 2, the crystalline mixture solid composition of ComparativeExample 1 and the hydrogenated isomaltulose powder of ComparativeExample 2 were dried at normal temperature under vacuum for 1 hour,placed in a closed sample container (made from Ag, 15 μl) and measuredwith a differential scanning calorimeter (DSC6200: Seiko InstrumentsCo., Ltd.) at a temperature range of 30 to 200° C. and a temperatureelevation rate of 4° C./min. The measurement results are shown in FIG.10. In FIG. 10, letters A, B, C and D denote the composition Y,composition X, crystalline mixture solid composition obtained in Example1 and crystalline mixture solid composition obtained in Example 2,respectively.

According to the present invention, there can be provided a crystallinemixture solid composition which rarely has moisture absorption, is easyto handle and dissolve, and comprises GPM and GPS-6 and/or a smallamount of GPS-1 in an extremely short period of time with small-scaleequipment by a process which can save power and does take much time andlabor.

What is claimed is:
 1. A crystalline mixture solid compositioncomprising α-D-glucopyranosyl-1,1-mannitol,α-D-glucopyranosyl-1,6-sorbitol and 0.01 to 1.5 wt % ofα-D-glucopyranosyl-1,1-sorbitol (the above wt % is based on the totalweight of the α-D-glucopyranosyl-1,1-mannitol,α-D-glucopyranosyl-1,6-sorbitol and α-D-glucopyranosyl-1,1-sorbitol). 2.The crystalline mixture solid composition of claim 1 produced by aprocess comprising the steps of supplying a composition comprising 50 to80 wt % of α-D-glucopyranosyl-1,1-mannitol, 1 to 50 wt % ofα-D-glucopyranosyl-1,6-sorbitol and 0.01 to 20 wt % ofα-D-glucopyranosyl-1,1-sorbitol into a kneader to knead and cool it soas to produce a composition, mixing the composition with a hydrophilicsolvent, and separating solid matter from a liquid (the above wt % isbased on the total weight of the α-D-glucopyranosyl-1,1-mannitol,α-D-glucopyranosyl-1,6-sorbitol and α-D-glucopyranosyl-1,1-sorbitol). 3.The crystalline mixture solid composition of claim 2 which comprises0.01 to 1.5 wt % α-D-glucopyranosyl-1,1-sorbitol.
 4. The crystallinemixture solid composition of claim 1 produced by a process comprisingthe steps of supplying a composition comprising 50 to 80 wt % ofα-D-glucopyranosyl-1,1-mannitol, 1 to 50 wt % ofα-D-glucopyranosyl-1,6-sorbitol and 0.01 to 20 wt % ofα-D-glucopyranosyl-1,1-sorbitol into a kneader having a thin and longcooling/kneading zone to knead and cool it, extruding the kneadedproduct through a punching plate, cooling and grinding the extrudedmolded product to produce a powdery crystalline mixture solidcomposition, mixing the composition with a hydrophilic solvent, andseparating solid matter from a liquid (the above wt % is based on thetotal weight of the α-D-glucopyranosyl-1,1-mannitol,α-D-glucopyranosyl-1,6-sorbitol and α-D-glucopyranosyl-1,1-sorbitol). 5.The crystalline mixture solid composition of claim 4 which comprises0.01 to 1.5 wt % α-D-glucopyranosyl-1,1-sorbitol.
 6. The crystallinemixture solid composition of claim 1 produced by a process comprisingthe steps of mixing a hydrophilic solvent with an aqueous solution whichcomprises 50 to 80 wt % of α-D-glucopyranosyl-1,1-mannitol, 1 to 50 wt %of α-D-glucopyranosyl-1,6-sorbitol and 0 to 20 wt % ofα-D-glucopyranosyl-1,1-sorbitol, and separating the formed precipitatefrom a liquid (the above wt % is based on the total weight of theα-D-glucopyranosyl-1,1-mannitol, α-D-glucopyranosyl-1,6-sorbitol andα-D-glucopyranosyl-1,1-sorbitol).
 7. The crystalline mixture solidcomposition of claim 6 which comprises 0.01 to 1.5 wt %α-D-glucopyranosyl-1,1-sorbitol.
 8. A crystalline mixture solidcomposition comprising 50 to 98 wt % of α-D-glucopyranosyl-1,1-mannitol,1 to 50 wt % of α-D-glucopyranosyl-1,6-sorbitol and 0.01 to 1.5 wt % ofα-D-glucopyranosyl-1,1-sorbitol (the above wt % is based on the totalweight of the α-D-glucopyranosyl-1,1-mannitol,α-D-glucopyranosyl-1,6-sorbitol and α-D-glucopyranosyl-1,1-sorbitol). 9.The crystalline mixture solid composition of claim 8 produced by aprocess comprising the steps of supplying a composition comprising 50 to80 wt % of α-D-glucopyranosyl-1,1-mannitol, 1 to 50 wt % ofα-D-glucopyranosyl-1,6-sorbitol and 0.01 to 20 wt % ofα-D-glucopyranosyl-1,1-sorbitol into a kneader to knead and cool it soas to produce a composition, mixing the composition with a hydrophilicsolvent, and separating solid matter from a liquid (the above wt % isbased on the total weight of the α-D-glucopyranosyl-1,1-mannitol,α-D-glucopyranosyl-1,6-sorbitol and α-D-glucopyranosyl-1,1-sorbitol).10. The crystalline mixture solid composition of claim 9 which comprises0.01 to 1.5 wt % α-D-glucopyranosyl-1,1-sorbitol.
 11. The crystallinemixture solid composition of claim 8 produced by a process comprisingthe steps of supplying a composition comprising 50 to 80 wt % ofα-D-glucopyranosyl-1,1-mannitol, 1 to 50 wt % ofα-D-glucopyranosyl-1,6-sorbitol and 0.01 to 20 wt % ofα-D-glucopyranosyl-1,1-sorbitol into a kneader having a thin and longcooling/kneading zone to knead and cool it, extruding the kneadedproduct through a punching plate, cooling and grinding the extrudedmolded product to produce a powdery crystalline mixture solidcomposition, mixing the composition with a hydrophilic solvent, andseparating solid matter from a liquid (the above wt % is based on thetotal weight of the α-D-glucopyranosyl-1,1-mannitol,α-D-glucopyranosyl-1,6-sorbitol and α-D-glucopyranosyl-1,1-sorbitol).12. The crystalline mixture solid composition of claim 11 whichcomprises 0.01 to 1.5 wt % α-D-glucopyranosyl-1,1-sorbitol.
 13. Thecrystalline mixture solid composition of claim 8 produced by a processcomprising the steps of mixing a hydrophilic solvent with an aqueoussolution which comprises 50 to 80 wt % ofα-D-glucopyranosyl-1,1-mannitol, 1 to 50 wt % ofα-D-glucopyranosyl-1,6-sorbitol and 0 to 20 wt % ofα-D-glucopyranosyl-1,1-sorbitol, and separating the formed precipitatefrom a liquid (the above wt % is based on the total weight of theα-D-glucopyranosyl-1,1-mannitol, α-D-glucopyranosyl-1,6-sorbitol andα-D-glucopyranosyl-1,1-sorbitol).
 14. The crystalline mixture solidcomposition of claim 13 which comprises 0.01 to 1.5 wt %α-D-glucopyranosyl-1,1-sorbitol.
 15. A crystalline mixture solidcomposition which is thin scale and comprisesα-D-glucopyranosyl-1,1-mannitol and α-D-glucopyranosyl-1,6-sorbitol. 16.The crystalline mixture solid composition of claim 15 which has aspecific surface area of 0.1 to 5.0 m²/g.
 17. The crystalline mixturesolid composition of claim 15 produced by a process comprising the stepsof mixing a hydrophilic solvent with an aqueous solution which comprises50 to 80 wt % of α-D-glucopyranosyl-1,1-mannitol, 1 to 50 wt % ofα-D-glucopyranosyl-1,6-sorbitol and 0 to 20 wt % ofα-D-glucopyranosyl-1,1-sorbitol, and separating the formed precipitatefrom a liquid (the above wt % is based on the total weight of theα-D-glucopyranosyl-1,1-mannitol, α-D-glucopyranosyl-1,6-sorbitol andα-D-glucopyranosyl-1,1-sorbitol).
 18. The crystalline mixture solidcomposition of claim 17 which has a specific surface area of 0.1 to 5.0m²/g.
 19. A process for producing a crystalline mixture solidcomposition, comprising the steps of supplying a composition comprising50 to 80 wt % of α-D-glucopyranosyl-1,1-mannitol, 1 to 50 wt % ofα-D-glucopyranosyl-1,6-sorbitol and 0.01 to 20 wt % ofα-D-glucopyranosyl-1,1-sorbitol into a kneader to knead and cool it soas to produce a composition, mixing the composition with a hydrophilicsolvent, and separating solid matter from a liquid (the above wt % isbased on the total weight of the α-D-glucopyranosyl-1,1-mannitol,α-D-glucopyranosyl-1,6-sorbitol and α-D-glucopyranosyl-1,1-sorbitol).20. The process for producing a crystalline mixture solid compositionaccording to claim 19, wherein the hydrophilic solvent is ethanol. 21.The process for producing a crystalline mixture solid compositionaccording to claim 19, wherein the hydrophilic solvent is an ethanolaqueous solution having a concentration of 60 to 90%.
 22. A process forproducing a crystalline mixture solid composition, comprising the stepsof supplying a composition comprising 50 to 80 wt % ofα-D-glucopyranosyl-1,1-mannitol, 1 to 50 wt % ofα-D-glucopyranosyl-1,6-sorbitol and 0.01 to 20 wt % ofα-D-glucopyranosyl-1,1-sorbitol into a kneader having a thin and longcooling/kneading zone to knead and cool it, extruding the kneadedproduct through a punching plate, cooling and grinding the extrudedmolded product to produce a powdery crystalline mixture solidcomposition, mixing the composition with a hydrophilic solvent, andseparating solid matter from a liquid (the above wt % is based on thetotal weight of the α-D-glucopyranosyl-1,1-mannitol,α-D-glucopyranosyl-1,6-sorbitol and α-D-glucopyranosyl-1,1-sorbitol).23. The process for producing a crystalline mixture solid compositionaccording to claim 22, wherein the hydrophilic solvent is ethanol. 24.The process for producing a crystalline mixture solid compositionaccording to claim 22, wherein the hydrophilic solvent is an ethanolaqueous solution having a concentration of 60 to 90%.
 25. A process forproducing a crystalline mixture solid composition, comprising the stepsof mixing a hydrophilic solvent with an aqueous solution which comprises50 to 80 wt % of α-D-glucopyranosyl-1,1-mannitol, 1 to 50 wt % ofα-D-glucopyranosyl-1,6-sorbitol and 0 to 20 wt % ofα-D-glucopyranosyl-1,1-sorbitol, and separating the formed precipitatefrom a liquid (the above wt % is based on the total weight of theα-D-glucopyranosyl-1,1-mannitol, α-D-glucopyranosyl-1,6-sorbitol andα-D-glucopyranosyl-1,1-sorbitol).
 26. The process for producing acrystalline mixture solid composition according to claim 25, wherein thehydrophilic solvent is ethanol.
 27. The process for producing acrystalline mixture solid composition according to claim 25, wherein thehydrophilic solvent is an ethanol aqueous solution having aconcentration of 60 to 90%.